The present invention relates to new selectively herbicidal compositions to combat grasses and weeds in crops of cultivated plants, especially in crops of cereals and rice which comprise a herbicide and a safener (antidote) and which protect the cultivated plants but not the weeds against the phytotoxic effect of the herbicide, and to the use of this composition for weed control in crops of cultivated plants.
When applying herbicides, the cultivated plants may also suffer severe damage owing to factors that include the concentration of the herbicide and the mode of application, the cultivated plant itself, the nature of the soil, and the climatic conditions such as exposure to light, temperature and rainfall.
To counteract this problem and similar ones, the proposal has already been made to use different compounds as safeners which are able to antagonise the harmful action of the herbicide on the cultivated plant, i.e. to protect the cultivated plant while leaving the herbicidal action on the weeds to be controlled virtually unimpaired. It has, however, been found that the proposed safeners often have a very specific action with respect not only to the cultivated plants but also to the herbicide, and in some cases also subject to the mode of application, i.e. a specific safener will often be suitable only for a specific cultivated plant and a specific class of herbicide or a specific herbicide. Compounds are known for example from WO 97/18712 which protect crop plants against the phytotoxic effect of specific herbicides. It has now been found that compounds of formula IIa 
wherein the substituents are as defined hereinafter, are suitable for the protection of crop plants against the phytotoxic effect of a compound of formula I 
Accordingly, the invention provides a selective herbicidal composition comprising, in addition to customary inert formulation assistants such as carriers, solvents and wetting agents, a mixture of
a) a herbicidally effective amount of a herbicide of formula I 
xe2x80x83and
b) to antagonise the herbicide, an antidotally effective amount of a safener of formula IIa 
xe2x80x83wherein
R32 is hydrogen, C1-C8alkyl or C1-C8alkyl substituted by C1-C6alkoxy or C3-C6alkenyloxy and
X1 is hydrogen or chlorine; or of formula IIb 
wherein E is nitrogen or methine;
R38 is C1-C4alkyl;
R39 is xe2x80x94CCl3, phenyl or phenyl substituted by halogen, and
R40 and R41 independently of one another are hydrogen or halogen;
or of formula IIc 
wherein R27 and R28 independently of one another are hydrogen or halogen, and
R29, R30 and R31 independently of one another are C1-C4alkyl; or of formula IId 
wherein A2 is a 
xe2x80x83group, R35 and R36 independently of one another are hydrogen, C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C6alkinyl, 
xe2x80x83or C1-C4alkyl substituted by C1-C4alkoxy or 
xe2x80x83or R35 and R36 together form a C4-C6alkylene bridge, which may be broken by oxygen, sulfur, SO, SO2, NH or xe2x80x94N(C1-C4alkyl)-; R37 is hydrogen or C1-C4alkyl;
R33 is hydrogen, halogen, cyano, trifluoromethyl, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, xe2x80x94COORj, xe2x80x94CONRkRm, xe2x80x94CORn, xe2x80x94SO2NRkRm or xe2x80x94OSO2xe2x80x94C1-C4alkyl;
Rg is hydrogen, halogen, cyano, nitro, C1-C4alkyl, C1-C4halogenalkyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, xe2x80x94COORj, xe2x80x94CONRkRm, xe2x80x94CORn, xe2x80x94SO2NRkRmxe2x80x94OSO2xe2x80x94C1-C4alkyl, C1-C6alkoxy, or C1-C6alkoxy substituted by C1-C4alkoxy or halogen, C3-C6alkenyloxy, or C3-C6alkenyloxy substituted by halogen, or C3-C6alkinyloxy, or R33 and R34 together form a C3-C4alkylene bridge, which may be substituted by halogen or C1-C4alkyl, or they form a C3-C4alkenylene bridge, which may be substituted by halogen or C1-C4alkyl, or they form a C4alkadienylene bridge, which may be substituted by halogen or C1-C4alkyl;
R34 and Rh independently of one another are hydrogen, halogen, C1-C4alkyl, trifluoromethyl, C1-C6alkoxy, C1-C6alkylthio or xe2x80x94COORj;
Rc is hydrogen, halogen, nitro, C1-C4alkyl or methoxy; Rd is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, xe2x80x94COORj or CONRkRm;
Re is hydrogen, halogen, C1-C4alkyl, xe2x80x94COORj, trifluoromethyl or methoxy, or Rd and Re together form a C3-C4alkylene bridge;
Rf is hydrogen, halogen or C1-C4alkyl;
Rx and Ry independently of one another are hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, xe2x80x94COOR38, trifluoromethyl, nitro or cyano;
Rj, Rk and Rm independently of one another are hydrogen or C1-C4alkyl; or
Rk and Rm together form a C4-C6alkylene bridge, which may be broken by oxygen, NH or xe2x80x94N(C1-C4alkyl)xe2x80x94;
Rn is C1-C4alkyl, phenyl, or phenyl substituted by halogen, C1-C4alkyl, methoxy, nitro or trifluoromethyl;
R38 is hydrogen, C1-C10alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, di-C1-C4alkylamino-C1-C4alkyl, halogen-C1-C8alkyl, C2-C8alkenyl, halogen-C2-C8alkenyl, C3-C8alkinyl, C3-C7cycloalkyl, halogen-C3-C7-cycloalkyl, C1-C8alkylcarbonyl, allylcarbonyl, C3-C7cycloalkylcarbonyl, benzoyl which is unsubstituted or substituted on the phenyl ring up to three times identically or differently by halogen, C1-C4alkyl, halogen-C1-C4alkyl, halogen-C1-C4alkoxy or C1-C4alkoxy; or furoyl, thienyl; or C1-C4alkyl substituted by phenyl, halogenphenyl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halogen-C1-C4alkylphenyl, halogen-C1-C4alkoxyphenyl, C1-C6alkoxycarbonyl, C1-C4alkoxy-C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkinyloxycarbonyl, C1-C8alkylthiocarbonyl, C3-C8alkenylthiocarbonyl, C3-C8alkinylthiocarbonyl, carbamoyl, mono-C1-C4alkylaminocarbonyl, di-C1-C4alkylaminocarbonyl; or phenylaminocarbonyl, which is unsubstituted or substituted on the phenyl ring up to three times identically or differently by halogen, C1-C4alkyl, halogen-C1-C4alkyl, halogen-C1-C4alkoxy or C1-C4alkoxy, or once by cyano or nitro, or dioxolan-2-yl which is unsubstituted or substituted by one or two C1-C4alkyl radicals, or dioxan-2-yl, which is unsubstituted or substituted by one or two C1-C4alkyl radicals, or C1-C4alkl which is substituted by cyano, nitro, carboxyl or C1-C8alkylthio-C1-C8alkoxycarbonyl; or a compound of formula IIf 
wherein R56 and R57 independently of one another are C1-C6alkyl or C2-C6alkenyl; or R56 and R57 together are 
R58 and R59 independently of one another are hydrogen or C1-C6alkyl; or R56 and R57 together are 
R60 and R61 independently of one another are C1-C4alkyl, or R46 and R47 together are xe2x80x94(CH2)6xe2x80x94;
R62 is hydrogen, C1-C4alkyl or 
xe2x80x83or R56 and R57 together are 
R63, R64, R65, R66, R67, R68, R69, R70, R71, R72, R73, R74, R75, R76, R77, and R78 independently of one another are hydrogen or C1-C4alkyl;
or a compound of formula IIg 
wherein R79 is hydrogen or chlorine and R80 is cyano or trifluoromethyl, or a compound of formula IIh 
wherein R81 is hydrogen or methyl, or of formula IIj 
wherein R82 is hydrogen, C1-C4alkyl, C1-C4alkyl substituted by C1-C4alkyl-X2xe2x80x94 or C1-C4halogenal-X2xe2x80x94, C1-C4halogenalkyl, nitro, cyano, xe2x80x94COOR85, xe2x80x94NR86R87, xe2x80x94SO2NR88R89 or xe2x80x94CONR90R91;
R83 is hydrogen, halogen, C1-C4alkyl, trifluoromethyl, C1-C4alkoxy or C1-C4halogenalkoxy;
R84 is hydrogen, halogen or C1-C4alkyl;
U, V, W1 and Z4 independently of one another are oxygen, sulfur, C(R92)R93, carbonyl, NR94, a 
xe2x80x83group, wherein R102 is C2-C4alkenyl or C2-C4alkinyl; subject to the proviso that a) at least one of the ring members U, V, W1 or Z4 is carbonyl, and a ring member adjacent to this or these ring members is either the 
xe2x80x83group, this group only occurring once; and
b) two adjacent ring members U and V, V and W1 and W1 and Z4 cannot simultaneously be oxygen;
R95 and R96 independently of one another are hydrogen or C1-C8alkyl; or
R95 and R96 together form a C2-C6alkylene group;
A1 is R99-Y1xe2x80x94 or xe2x80x94NR97R98;
X2 is oxygen or xe2x80x94S(O)s;
Y1 is oxygen or sulfur;
R99 is hydrogen, C1-C8alkyl, C1-C8halogenalkyl, C1-C4alkoxy-C1-C8alkyl, C3-C6alkenyloxy-C1-C8-alkyl or phenyl-C1-C8-alkyl, wherein the phenyl ring may be substituted by halogen, C1-C4-a, trifluoromethyl, methoxy or methyl-S(O)sxe2x80x94, C3-C6alkenyl, C3-C6halogenalkenyl, phenyl-C3-C6alkenyl, C3-C6alkinyl, p-C3-C6alkinyl, oxetanyl, furyl or tetrahydrofuryl;
R85 is hydrogen or C1-C4alkyl;
R86 is hydrogen, C1-C4alkyl or C1-C4alkylcarbonyl;
R87 is hydrogen or C1-C4alkyl; or
R86 and R87 together form a C4 or C5alkylene group;
R88, R89, R90 and R91 independently of one another are hydrogen or C1-C4alkyl; or R88 and
R89 or R90 and R91 are independently of one another C4 or C5alkylene, in which a carbon atom may be substituted by oxygen or sulfur, or one or two carbon atoms by xe2x80x94NR100xe2x80x94;
R92 and R100 independently of one another are hydrogen or C1-C8alkyl; or
R92 and R93 together are C2-C6alkylene;
R94 is hydrogen or C1-C8alkyl;
R97 is hydrogen, C1-C8alkyl, phenyl, phenyl-C1-C8alkyl (in which the phenyl ring may be substituted by fluorine, chlorine, bromine, nitro, cyano, xe2x80x94OCH3, C1-C4alkyl or CH3SO2xe2x80x94), C1-C4alkoxy-C1-C8alkyl, C3-C6alkenyl or C3-C6alkinyl;
R98 is hydrogen, C1-C8alkyl, C3-C6alkenyl or C3-C6alkinyl; or
R97 and R98 together are C4 or C6alkylene, in which a carbon atom may be substituted by oxygen or sulfur, or one or two carbon atoms by xe2x80x94NR101xe2x80x94;
R101 is hydrogen or C1-C4alkyl;
r is 0 or 1; and
s is 0, 1 or 2, or a compound of formula IIk 
wherein R103 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl, C3-C6alkenyl or C3-C6alkinyl; and R104, R105 and R106 are independently of one another hydrogen, C1-C6alkyl, C3-C6cycloalkyl or C1-C6alkoxy, subject to the proviso that one of the substituents R104, R105 or R106 is different from hydrogen, or a compound of formula IIq 
The alkyl groups occurring in the substituent definitions may be straight-chained or branched, and may for example be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, as well as their branched isomers. Alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, and alkylsulfinyl groups are derived from the said alkyl groups. Halogen is usually fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. In substituents such as xe2x80x94NRkRm, the alkyl radicals may be the same or different. In the preferred embodiment, they are the same. The term xe2x80x9csubstitutedxe2x80x9d may mean in the context of the present invention monosubstituted and, as far as possible, also polysubstituted.
The compound of formula 1 is described in EP-A-0 507 171. Compounds of formulae IIa, IIb, IIc, IId, IIf, IIg, IIh, IIj, and IIk are known from U.S. Pat. No. 5,041,157, U.S. Pat. No. 5,541,148, U.S. Pat. No. 5,006,656, EP-A-0 094 349, EP-A-0 551 650, EP-A-0 268 554, EP-A-0 375 061, EP-A-0 174 562, EP-A-492 366, WO 91/7874, WO 94/987, DE-A-19612943, WO 96/29870, WO 98/13361, and WO 97/18712. The compound of formula IIq is described in DE-A-4331448.
The compound of formula I may preferably be used according to the invention with the safeners of formulae IIa, IIb and IIc.
A very especially preferred composition according to the invention comprises the compound of formula I and the safener of formula IIa, wherein X1 is chlorine and R22 is xe2x80x94CH(CH3)C5H11xe2x80x94n.
Especially preferred compounds of the formulae and IIa toliq are listed in the following tables (formula IIe is the preferred compound of formula IId, and formulae IIm, IIn, IIo and IIp are the preferred compounds of formula IIh):
The invention also relates to a method of selectively controlling weeds in crops of cultivated plants, which comprises treating said cultivated plants, the seeds or seedlings or the crop area thereof, concurrently or separately, with a herbicidally effective amount of the herbicide of formula I and, to antagonise the herbicide, an antidotally effective amount of the safener of formula IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq.
Crop plants which may be protected by the safeners of formula IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq from the damaging effect of the herbicides mentioned hereinbefore are in particular cereals and rice. Crops will also be understood as meaning those crops that have been made tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods.
The weeds to be controlled may be monocot as well as dicot weeds, typically Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, lpomoea, Chrysanthemum, Galium, Viola, and Veronica.
Crop areas will be understood as meaning the areas already under cultivation with the cultivated plants or seeds thereof, as well as the areas intended for cropping with said cultivated plants.
Depending on the end use, a safener of formula II can be used for pretreating seeds of the crop plants (dressing of seeds or seedlings) or it can be incorporated in the soil before or after sowing. It can, however, also be applied by itself alone or together with the herbicide postemergence. Treatment of the plant or the seeds with the safener can therefore in principle be carried out irrespective of the time of application of the herbicide. Treatment can, however, also be carried out by simultaneous application of the phytotoxic chemical and safener (e.g. as tank mixture). The concentration of safener with respect to the herbicide will depend substantially on the mode of application. Where a field treatment is carried out either by using a tank mixture with a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of safener to herbicide will usually be from 1:100 to 1:1, and preferably 1:50 to 5:1.
In field treatment it is usual to apply 0.001 to 5.0 kg safener/ha, preferably 0.001 to 0.5 kg safener/ha.
The rate of application of herbicide is usually in the range from 0.001 to 2 kg/ha, but will preferably be from 0.005 to 1 kg/ha.
The compositions of this invention are suitable for all methods of application commonly used in agriculture, including preemergence application, postemergence application and seed dressing.
For seed dressing, 0.001 to 10 g of safener/kg of seeds, preferably 0.05 to 2 g of safener/kg of seeds, is usually applied. If the safener is used in liquid form shortly before sowing to effect soaking, then it is preferred to use safener solutions that contain the active ingredient in a concentration of 1 to 10000 ppm, preferably of 100 to 1000 ppm.
For application, it is expedient to process the safeners of formula II, or mixtures of the safeners of formula II and the herbicides of formula I, together with the customary assistants of formulation technology to formulations, typically to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates or microcapsules.
Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. The formulations are prepared in known manner, for example by homogeneously mixing or grinding the active ingredients with liquid or solid formulation assistants, typically solvents or solid carriers. Surface-active compounds (surfactants) may additionally be used for preparing the formulations. Suitable solvents and solid carriers for this purpose are described in WO 97/34485 on page 6.
Depending on the herbicide of formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, nonionic, and cationic surfactants are listed in WO 97/34485 on pages 7 and 8. Also the surfactants customarily employed in the art of formulation and described, inter alla, in xe2x80x9cMc Cutcheon""s Detergents and Emulsifiers Annualxe2x80x9d MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., xe2x80x9cTensid-Taschenbuchxe2x80x9d (Handbook of Surfactants), Carl Hanser Verlag, MunichNienna, 1981, and M. and J. Ash, xe2x80x9cEncyclopedia of Surfactantsxe2x80x9d, Vol I-III, Chemical Publishing Co., New York, 1980-81 are suitable for manufacture of the herbicides according to the invention.
The herbicidal compositions will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of compound mixture of the compound of formula I and the compounds of formula IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq, from 1 to 99.9% by weight of a solid or liquid formulation assistant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
Whereas it is customarily preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The compositions may also contain further ingredients, such as: stabilisers, e.g. where appropriate epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil, or soybean oil); antifoams, typically silicone oil; preservatives; viscosity regulators; binders; and tackifiers; as well as fertilisers or other chemical agents. Different methods and techniques may suitably be used for applying the safeners of formula II or compositions containing them for protecting cultivated plants from the harmful effects of herbicides of formula I, conveniently the following:
i) Seed Dressing
a) Dressing the seeds with a wettable powder formulation of the active ingredient of formula II by shaking in a vessel until the safener is uniformly distributed on the surface of the seeds (dry treatment). About 1 to 500 g of active ingredient of formula IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq (4 g to 2 kg of wettable powder) are used per 100 kg of seeds.
Dressing the seeds with an emulsifiable concentrate of the active ingredient of formula IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq according to method a) (wet treatment).
c) Dressing by immersing the seeds in a mixture containing 100-1000 ppm of active ingredient of formula IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq for 1 to 72 hours and, where appropriate, subsequently drying them (seed soaking).
In keeping with the natural environment, the preferred method of application is either seed dressing or treatment of the germinated seedlings, because the safener treatment is fully concentrated on the target crop. Usually 1 to 1000 g, preferably 5 to 250 g, of safener is used per 100 kg of seeds. However, depending on the method employed, which also permits the use of other chemical agents or micronutrients, the concentrations may deviate above or below the indicated limit values (repeat dressing).
ii) Application as a Tank Mixture
A liquid formulation of a mixture of safener and herbicide (reciprocal ratio from 10:1 to 1:100) is used, the concentration of herbicide being from 0.005 to 5.0 kg/ha. This tank mixture is applied before or after sowing.
iii) Application in the Furrow
The active ingredient of formula IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq formulated as emulsifiable concentrate, wettable powder or granulate is applied to the open furrow in which the seeds have been sown. After covering the furrow, the herbicide is applied pre-emergence in conventional manner.
iv) Controlled Release of Compound
The compound of formula Formel IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq is applied in solution to a mineral granular carrier or to polymerised granules (urea/formaldehyde) and then dried. A coating can then be applied (coated granules) that allows the herbicide to be released at a controlled rate over a specific period of time.
Particularly preferred formulations are made up as follows:
(%=per cent by weight)
Emulsifiable Concentrates:
Compound mixture: 1 to 90%, preferably 5 to 20%
Surfactant: 1 to 30%, preferably 10 to 20%
Liquid carrier: 5 to 94%, preferably 70 to 85%
Dusts:
Compound mixture: 0.1 to 10%, preferably 0,1 to 5%
Solid carrier: 99.9 to 90%, preferably 99,9 to 99%
Suspension Concentrates:
Compound mixture: 5 to 75%, preferably 10 to 50%
Water: 94 to 30%, preferably 88 to 20%
Surfactant: 1 to 30%, preferably 2 to 20%
Wettable Powders:
Compound mixture: 1 to 90%, preferably 10 to 80%
Surfactant: 1 to 30%, preferably 10 to 20%
Solid carrier: 5 to 95%, preferably 15 to 90%
Granulates:
Compound mixture: 0.1 to 30%, preferably 0,1 to 15%
Solid carrier: 99.5 to 70%, preferably 97 to 85%
The invention is illustrated by the following non-limitative Examples.
Formulation Examples for mixtures of herbicides of formula I and safeners of formula IIa, IIb, IIc IId, IIf, IIg, IIh, IIj, IIk or IIq (%=per cent by weight)
mixture C9-C12 
Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
The solutions are suitable for use in the form of microdrops.
The compound is throughly mixed with the adjuvants and this mixture is ground in a suitable mill to give wettable powders which can be diluted with water to give suspensions of any desired concentration.
(AE 0.1-1 mm)
such as CaCO3 or SiO2 
The compound mixture is dissolved in dichloromethane, the solution is sprayed on to the carrier, and the solvent is removed under vacuum.
(AE 0.1-1 mm)
such as CaCO3 or SiO2 
The finely ground active substance is uniformly applied in a mixer to the carrier moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
The compound is mixed and ground with the adjuvants, and the mixture is moistened with water. This mixture is extruded and then dried in a stream of air.
Ready for use dusts are obtained by mixing the active ingredient with the carriers on a suitable mill.
The finely ground active substance is intimately mixed with the adjuvants to give a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
It is often expedient to formulate the compound of formula I and the components of formulae IIa to IIq individually and only to combine them shortly before application in the applicator in the desired mixture ratio as tank mixture in water.